Chlorinated compound and process of making same.



Je W1 AYLSLWORTH., GHLORINATBD GOMPOUND AND PROCESS 0F MAKING SAME.

Patented Mar. 2, www

APPLICATION FILED MAY 9, 1907.

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JONAS w. AYLSWORTH, or EAST ORANGE, NEW JERSEY, ASSIGNOR, BY DIRECT AND MESN'E ASSIGNMENTS, To rIRErRoor PRODUCTS COMPANY, A coRPolniTIoN or NEW JERSEY.

'CHLORINATED COMPOUND AND PROCESS 0F MAKING- Specification of Letters Patent.

ratented Maren a, maar Application mea may e, 1907. semi No. erases.

To all whom it 'may concern: Y

Be it known that I, JONAS W. AYLSWORTH, a citizen of the United States, residing at 223 Midland avenue, East Orange, county of Essex, and State of New Jersey, have Vinvented certain new and useful Processes of Making Chlorin Compounds and Products Thereof, of which the following is a description.

ln the manufacture of sodium or potassium; and of soda and potash by the elec.- trolysis of fused chlorids of those metals or solutions of such chlorids, large amounts of chlorin gas are evolved which not only to a very considerable extent have been regarded as ywaste produc-ts, but the effective disposition of such gas has presented a serious problem, owing to its noxious character. It is true that to some extent the chlorin gas has been used in the manufacture of bleaching powder, but the demand for bleaching powder is not large enou h to warrant the use of all ofthe chlorin evo ved in the alkali manufacture for that purpose.

The object of my invention is to provide an effective rocess bymeans of which chlorin gas obtained) inconnection with electrolytic alkali manufactured from chlorids orfrom any and copious source may be effectively use for the reduction of hydrochloric acid (for which` a -very large demand exists) while atthe same time l may obtain as a by-produot a material that may be put to a number of industrial uses, as 'will more fully hereinafter describe. c,

My invention is based on the fact that when chlorin gas, preferably in the presence of heat and under ressure, is brought in contact with a suitabv e organic body, either liquid or capable of becoming liquid by heat, such as hydrocarbon oils, naphthalene, araffin, stearic acid, and similarbodies, t e organic material becomes gradually chlorinated, resulting in the formation of chlorin addition and substitution roducts and of hydrochloric acid gas. Wit such a reaction, for every atom of chlorin which is substituted. for h dro en in the organic material, one molecu e of hydrochloric acid gas is produced. Where it is not important to 'obtain f a chlorinated by-product, and wherethe manufacture of hydrochloric acid is principally desired, the chlorin gas under lheat and pressure, may be brought into contact with an organic material, such as Tosin, oleic Lacid and various gummy bodies, maintained ina liquid state by heat, and the ychlorination may be permitted to progress until about onehalf of the substitutable hydrogen has been replaced by the chlorin, after which the partially chlorinated roduct thus obtained is decomposed at a higher temperature, resulting in the productionof hydrochloric -acid gas and tarry` residues as by-products. V'll prefer, however, the simplechlormatingrocess, not only because it is ycapable of eing more effectively carried out, but also because chlorinated materials are obtained which can be utilized effectively in the arts. For example, l have discovered that if naphthalene is hlghly chlorinated it can be converted into -a very effective fireproofing material for the treatment of wood and fabric, being in this respect superior to any re roof materia-lof which l have knowledge. uch'chlorinated naphthalene will also be very cheap and can be readily handled for saturatin or otherwise treating the material desire For the proper chlorination of the material, it is necessary that the chlorin gas should be brought in contact with the material in such a Way as to present a relatively enormous surface, since the chlorination progresses very slowly toward. the end of the o eration. It is also important that as the clilorinating effect of the chlorin gas is-gradually reduced by admixture therewith of gradually increasing amounts of hydrochloric acid gas, itshoul encounter the material carrying the maximum value of the substitutable hydrogen; or in other words, the chlorin gas and the material should be slowly progressed in op osite directions-and in contact with one anot er.

In carrying the invention into effect, 'l prefer to make use of a series of ohlorinating vessels of such a character that a very Vlarge surface of the hydrocarbon material in each will be exposed to the chlorin gas, and I slowly progress the chlorin under pressure successively throu h the said chlorinatin vessels, while at t esame time the liqui material is slowly progressed in the opposite direction throu h the chlorinating vessels, suitable means lieing provided for maintainin the desired .temperature within Ithe chorinatmg vessels, and a. suitable pressure being maintained therein to effect the chlorination of the material, the degree of such temperature and the extent of such' pressure depending somewhat upon the llo roo ros

particular material under treatment. Provision is made for drying the chlorin gas.

before entering the apparatus, in order that it may be safely compressed 5 ump or comlpressor, although this will not e necessary sufficient pressure can be develo ed within the electrolytic ap aratus in whic the primary reactions ta e place. Provision is also made for properly collecting the evolved hydrochlorlc acid gas, preferably by absorbing the same in water in an ordinary acid condensing tower. Finally, provision is made for collecting the chlorinated material (assuming that the chlo-y directed to the accompanying drawin s, forming part of this specification, and in W ich- Figure 1, is a diagrammatic view, illustrating a suitable ap aratus for carryin the process .into effect, Fig. 2, an enlarge sectional view of one of the chlorinating vessels which I prefer to use, Fig. 3, a sectional view on the -one of the pan-like artitions employed in the'chlorinating vesse s.

In all of thev aboveviews, corresponding arts are represented by the same numerals of reference.

1 represents diagrammatically any suitable electrolytic apparatus for use in alkali manufacture from chloridsthereof; for instance the apparatus used with the so-called Acker process, and wherein the effect of electrolysis is to generate chlorin gas as a byproduct. It will be understood of course that the chlorin gas may be obtained from any other cheap and copious source but the electrolytically generated chlorin is preferred as being more active` in its reaction u on organic matters. The chlorin is led t ough pipe 2, into a suitable drying aplparatus 3 of any desired type, whereby t e gas may' be made erfectly dry, so as to of its being e ectively compressed. t will be'understood that when the chlorin gas can be generated under sufficient pressure so as to not'require the use'of pumping apparatus, the drying device 3 and vpump 4 may be omitted. From the drier 3 the gas is led to the compressor 4, by which it is forced under the desired pressure through one or more chlorinating chambers 5, three beinlshown.

I prefer to make use of a series of c orinatin a suitable line 3-3 of Fig. 2, and Fig. 4, a front view of A ermit.

ing chambers, in order that a higher temperature may be maintained in the chamber nearer the compressor 4, and successively lower temperaturesin the others, so that the material as it becomes gradually more and more chlorinated will be subjected to suc' cessively hi her tem eratures. In this way I obtain the est resu ts because as the hydrocarbon material becomes gradually chlorinated, the rate at which the chlorination is effected is reduced, but by employing successively higher temperatures in the succeeding chlorinating vessels, the rate Aof chlorination willbe more nearly uniform.

Each chlorinatingchamber is formed of a vessel 6, having a removable top 7, and each beingheated independently in any suitable way, as for exam le, by a steam jacket 8. Each of the cham ers 6 is made of lead or earthen ware, or other suitable material 85 not affected by the chlorin andca able ,of withstanding the pressures used. e chlorinating chambers are of such a character that the liquid hydrocarbon material flowing throu h the same will be subjected to relatively arge areas of surface contact with the chlorin gas', and for this urpose I prefer to arran'ge within each c orinating chamber a series of pan-like partitions 9 having -the general form of an inverted pan, mounted one above the other and supported in any suitable way, as for example, y the rods 10x, 10.v Each of the partitions or inverted pans is formed with a recess 11 in its rim, having a notch 12 therein, and these recessed portions are staggered as shown, whereby the gas entrapped beneath the bottom partition will be permitted to escape slowly through the notch 12 thereof, into the partition immediately above ther same, and in turn escape through the o posite edge of the second artition to the -t 1rd artition, and so on, t oughout the series. n this way, I not only. maintain large bodies of chlorin gas submerged below the-level of the liquid material, so as to resent extended, areas of surface contact of te gas therewith, but I cause the gas to travel a relatively great distance in passing through each chlorinating apparatus so as to act on the liq- 115 uid materia in the most effective manner. The pipe 13 from the pump 4 leads into the first chlorinating chamber and delivers the gas under the lowermost partition 9 thereof, while the gas esca es throughthe ipe 14 120 which leads from the hood 9 located) above the top partition 9 and extends in a similar manner below the lowermost partition of the second chlorinating chamber from the erases partitions thereof. From the third chlorin-' ating cham-ber the liquid passes by a pipe 21 into the upper end of the second chlorinating chamber and' from the latter it passes by a pipe 22 into the upper end of the first chlorinating chamber. From the lower end of the rst chlorinating chamber, the chlorinated liquid passes by a pipe 23 into either of the pair of receiving tanks 24, valves 25 permitting the li uid to be directed into either of said tanks. Cln order to free the chlorinated liquid of any dissolved chlo-rin, I provide pipes 26, havingperforated lower ends 27, and by means of which air may be injected into the liquid escaping throu h a vent 28. During this treatment, the chlorinated ma teria-l in either of said tanks 24 is heated somewhat higher than its temperature during the chlorination, (for instance, by steam jackets as shown surrounding said tanks) and also, the chlorinated material, by the same means, is maintained in a heated condition at all times in said tanks, so as to be kept iiuid and lpermit of ready handling. From either of t e tanks the liquid may be drawn od through valved pi es 29. Steam for heating the steam jac rets of the several chlorinating chambers may be admitted by pipes 30, although as stated, the chambers may be heated in other ways.

In order to maintain the desired pressure Within the apparatus, I prefer to employ an ordinary relief valve 31 mounted in the pipe 23 which does not open until a predetermined pressure is reached, and I place a similar relief valve 32 in the pipe 16, which opens only 'when a predetermined pressure is reached. These relief valves are so adjusted that when the desired pressure exists within the apparatus the level of the liquid in the third and uppermost chlorinating chamber will be maintained, somewhat above the uppermost partition therein, so as to remove the possibility of the liquid being forced through the pipe 16 by the gas pressure.

In operation, a suitable organic material either norm ally liquid or rendered so by heat, of which an excellent example is naphthalene is forced by the pump 19 against the pressure within the apparatus so as to iill the chlorinating chambers and slowly pass the relief valve 31, into one or the other of the receiving tanks 24. Until the gas enters the apparatus the liquid will, therefore, ill the pipes 14 and 15, and so much of the pipe 13 as the compression of air therein will permit. The

chlorin gas is now forced in the apparatus by the pump 4 from the tower 3, and enters the pipe 13, displacing the air and li uid therein, said gas escaping into the s ace eneath the lowermost partition of the rst chamber and driving out the air before it, gradually rising into the successive partitions, and escaping through the pipe 14 into the second chlorinating chamber, where the same action takes place. In thus passing slwly into contact the temperature and pressure Within the ap- I paratus, the material gradually becomes chlorinated and reactions take place between the chlorin and,the substitutable hydrogen of the hydrocarbon to form hydrochloric acid, so that by the time the gas leaves the apparatus through the pi e 16, it will be substantially pure hydrochlbric 4acid gas, the heat and pressure employed accelerating the reaction and causing it to be complete with total absorption of chlorin.-r This gas enters the condensing tower 17, where it is absorbed in water in the usual Way. The chlorinated material entering one of the receiving tanks 24 will gradually fill the same', and when this tank is filled it is directed into the other tank.. While the second tank is air is blown into the chlorinated material already received in the first tank, so as to remove any dissolved chlorin and the material thus treated is drawn out by the pipe 29, and the tank again made ready for receiving the chlorinated material from the first of the chlorinating chambers. Instead of treating the chlorinated material with air, as explained, it may be washed or subjected to other known operations. For the effective chlorination of naphthalene, as explained, a pressure of from ten to fifty pounds or more per squareV inch may be maintained within the apparatus. I iind, in fact, that naphthalene even under atmospheric pressure, and when subjected to a temperature of only 212o F. absorbs chlorin quite rapidly (the l rate, according to my determinations, being about one gram per square inch per hour) but 4 under the same conditions the rate of absorption of chlorin near the completion of theoperation is much slower, being in fact, only about 15 If, however, the temperature and pressure are raised within safe limits,-having in l mind the prevention of decomposition of the naphthalene, or other hydrocarbon, aswell as l the safetv of the apparatus-the rapidity of absorptidn will be increased. For commerl ture in excess of 300 F. or a pressure exceedl ing fifty pounds per square inch. As pre'- viously' stated, the maximum temperature i preferably exists in the chlorinating chamber i nearest the compressor 4, the temperatures in the preceding chamber being successively re- With the liquid material under the effect of cial operation, I would not advise a temperabeing filled with the chlorinated material,

gram per square inch per hour.

duced, and the pressure of course being the same, or substantially so, in all. Since the chlorin is forced into the chlorinating vessels at one endfof the series under pressure and melted naphthalene is forced in under pressure at the other end of the series, the relief valves 31 and 32 will provide for the maintenance of a substantial uniformity of pressure throughout.

I find in the chlorination of naphthalene, that the addition of a small percentage of chlorid of antimony to the material in course of treatment greatly facilitates the chlorinating, operation, owing to its catal tic effect as a chlorin carrier. Naphtha ene that has been completely chlorinated by the operations above described, yields a solid wax-like material, capable of being sublimed without decomposition at a temperature of about 600 F., having a melting point of 262 F., and a specific gravity of about 1.850. It is soluble in chloroform, carbontetrachlorid and naphtha. The completely chlorinated product contains about 68% of chlorin. With other organic materials, the pressures and temperatures may be somewhat varied, depending upon the 'character of the material treated. When it is not important that chlorinated final product should .be obtained and where a larger yield of hydrochloric acid is desired, a less resistant organic material such as oleic acid may be passed through the apparatus and the chlorination be permitted to pro ress until about one-half'of the substitutab e hydrogen has been replaced by chlorin. lhe hydrochloric' acidl evolved from such a material will be directed to the condensing tower 17, as alieady described, but instead of pet e chlorinated or partially c oservin Ir rinated material as a finished roduct, it be decomposed by the apphcation of a ma higher tem rature, so as to result in a further pro uction of hydrochloric acid with a tarry residue. I prefer, however, to treat a hydrocarbon material which will result ina substantially non-decomposable chlorinated hydrocarbon, such as naphthalene, ,because such a chlorinated material ma be used commercially in the arts. For instance, I have discovered that chlorinated naphthalene is a very valuable iireproofing material, and I have claimed such use of the same iii an application Serial No. 372,688 filed on even date herewith. I do not claim herein the specific process described, of partially chlorinating the hydrocarbon material and then decomposing the saine, as I intend to make that specific process the subject of a separate application for Letters Patent.

Having now described my invention, what I claim as new and desire to secure by Letters Patent is as followsz 1. The rocess of -manufacturin hydrochloric acid, which consists in e ecting a reaction under heat and pressure between chlorin gas and naphthalene, substantially as and for the purposes set forth.

2. The process of manufacturing hydrochloric acid, which consists in maintaining a ysuitable li uid organic material under pressure in a cated condition and in forcing chlorin as through the liquid material, substantia y as set forth.

3. The process of manufacturing hydrochloric acid, which consists in maintaining a suitable liquid or anic material under pressure in a heate -condition, and in submerging within the same a body of chlorin gas having a relatively large surface area as compared to its volume and presenting an extended area to the action of the liquid material, substantially as set forth.

4. The process of manufacturing hydrochloric acid, which consists in maintaining a' liquid organic materialin a heated condition under pressure and in submerging beneath the same a series of bodies of chlorin gas, each of extended. area as compared to lits volume, substantially as set forth.

5. The process of. manufacturing hydrochloric acid, which consists in maintaining a liquid organic material under heat and pressure, Vin submerging beneath the sainel a series. -of bodies of chlorin gas', each of eX- tended area as compared to its volume, and in causing the chlorin to sively throughout the series, set forth..

6. The rocess of manufacturing hydrochloric acid, which consists in slowly progressing a body of liquid organic materi under pressure 1n one direction, and in slowly progressing chlorin gas through the liquid material in the other direction, substantially as set forth.

7. The rocess of manufacturing hydrosubstantially as chloric aci which consists in slowlr moving4 in one direction a confined body o a liqui organic material maintained in a heated-condition, in slowly ino g in the opposite direction through the liquid a' stream of chlorin gas, and in causing the 'chlorin to form shallow fiattened layers within the liquid so as to present to the latter an extended area as compared to its volume, substantially as set forth.

8. The process of manufacturing hydrochloric acid, which consists in slowlyr movingi in one direction a confined body o a liqui organic. material maintained in a heated condition under ressure, in slowl i movin in the opposite rect'on through the liqui a stream of chlorin gas, and in absorbing in water the hydrochloric acid thereby produced, substantially as set forth.

9. The rocess of manufacturing hydrochloric aci which consists in slowly moving in one direction a confined body of a suitable organic material maintained under heat and progress succesiio pressure, in forcing a stream of chlorin as through the liquid in the opposite direction thereby effecting a chlorination of the liquid, and in finally freeing the chlorinated liquid of dissolved chlorin,v substantially as set g forth.

10. The process of manufacturing hydrol chloric acid, which consists in slowly moving l in one direction a confined body of a suitable organic material maintained under heat and pressure, in forcing a stream of chlorin gas through the material in the opposite' direction, thereby effecting a chlorination of the material, and in finally blowing air through the chlorinated material, so as to free the same of dissolved chlorin, substantially as set forth.

11. The process of utilizing the chlorin gas evolved in electrolytic alkali manufacture, which consists in drying electrolytic chlorin and in maintaining the saine under pressure Within a body of liquid organic material to thereby form hydrochloric acid, substantially as set forth.

12. The process of utilizing the chlorin gas evolved in electrolytic alkali manufacture, which consists in electrolytic ciilorin and in maintaining the same under' pressure within a body of liquid organic' material maintained in a heated condition, tofx thereby form hydrochloric acidi,1 as and for the purposes set forth.

13. The process of utilizing the chlorin gas evolved in electrolytic alkali manufacture, v which consists 'in drying electrolytic chlorin and in maintaining the sam-e? under pressure Within a body of liquid organic material maintained under heat and pressurev to l thereby form hydrochloric acid, as and for the' purpose set forth. E

14. The process of utilizing the chlorin gas t evolved in electrolytic alkali manufacture, Which consists in drying the gas and in maintaining the same under pressure; within a body of heated naphthalene, maintained under pressure to thereby form hydrochloricV acid and chlorinated naphthaleneas and for the purposes set forth.

16- The process of utilizing the'chlorin gas, evolved in electrolytic alkali manufacture, which consists in drying the gas, in forcing the same under pressure into a body ofliquid organic material maintained under heat and pressure, to thereby form hydrochlbric. acid, and in finally absorbing the hydrochloric acid in Water, substantially asset forth.

17. Tl'ieprocess of manufacturing hydrochloric acid, which consists in slowly progressing a body of' liquid organic material under pressure inione direction, in subjectingl the liquid to successively increasing temperatures asl it progresses, and in slowly pro gressing chlorin gas through theiliquid im'che; other direction, substantially asset fortln. Y 18. As.v a new product, a chlorinated? derivative of naphtlialene, said derivativewbeing a Waxlike body, containing abouti68 pen'cent.

' of chlorin, subli'mirig without decomposiirion at a temperaturei of about 6009*" F., melting at about-262 Flhaving a specific of about 1.850 andbeing soluble-inichlcnolorm,

1 carbontetrachlbniid and naphtha.

This; specification signed and witnessed this 7 the day oflllay, 1907.

HORAS W.,AYI'JSVSl@lH. Witnesses:

Einem Duin., Exam E. Lewis. 

